Certain substituted aminothioethoxy pyridines



United States Patent 3,535,328 CERTAIN SUBSTITUTED AMINOTHIOETHOXYPYRIDINES James Zielinski, Kenilworth, N.J., assignor to Esso Re- 1search and Engineering Company, a corporation of Delaware No Drawing.Filed Sept. 1, 1967, Ser. No. 664,944

Int. Cl. C07d 31/42 U.S. Cl. 260-296 52 Claims ABSTRACT OF THEDISCLOSURE This disclosure relates to new monoand poly-substitutedpyridine derivatives, their methods of preparation and use aspesticides. A broad classification of preferred pyridine derivatives ischaracterized by the following alternative formulae:

where n can be an integer of from 1 to 4, and X and (ADZ) can occupy anyring position of from 2 to 6. When n is 1, X can be hydrogen, carboxyl,imido, dialkylamino, keto, alkylthio, cycloalkyl, phosphoramido, ureido,haloalkyl such as as trihalomethyl, halogen such as chlorine, fluorine,or iodine, hydroxyl, amino, nitro, aldehydo, arylthio, alkoxyl,phenoxyl, carbamyl, alkylsulfoxide, nitrile, amido, alkylamino, nitroso,mercapto, alkyl, sulfonamido, benzyloxy, alkylsulfone, etc. When n isgreater than 1, X can be the same or a combination of any of the abovesubstituents. Relative to the ADZ substituent, (I) A can be 0, NH, NR,NR S(O CR O--, 0R etc., (II) D can be any of the following: (a) (CH (b)(CH ),,G(CH where n is 1-6 and G is NR, 0, S, SO, S0 and F G, (c)

Where n is 1 or 2, (d) (CH ),,(C=C) (CH where n is 1 or 2, and (e) analkyl linkage having from 1 to 6 carbon atoms and a substituent (R)located at the terminal, or any adjacent, carbon atom; (III) and Z canbe: (1) a substituted amino group of the formula where the L moiety mayor may not be the same and is defined alternatively as RI, M

where M is NR, S, or O and R is NR OR, SR, or haloalkyl, or as I IIP(OR)2, P(OR)2 SOR, or SO R; (2) NR N+R SR, or OR; (3) when X is amino,chloro, or alkoxy, and n is 1, Z is NHR, N+R SR, or OR (A and D being asdescribed); (4) when X is amino, chloro, bromo, alkoxy, or nitro and nis 1 and A is NH, Z is NHR, N+R SR, or OR (D being as before); (5) whenX is phenoxy and n is 1 and A is CH Z is NHR, N+R SR, or OR (D being asdescribed); (6) when X is hydrogen and n is 4 and A is S, Z is NR SR, orOR; (7) OL [L being as in (III(1))] except that A cannot be oxygen; (8)SL [L being as in (III(1))]; and (9) phenyl, substituted phenyl,alkenyl, alkynyl, haloalkyl. The moiety R wherever it appears above ismeant to include any of the following: hydrogen, alkyl, cycloalkyl,aralkyl, aryl, alkenyl, alkynyl, or substituted alkyl whosesubstitutents are as defined by X above.

DESCRIPTION OF THE INVENTION This invention relates to new compositionshaving pesticidal activity, comprising both monoand poly-substitutedpyridine derivatives.

A number of substituted pyridine derivatives, however, are already knownin the prior art. Exemplary of such known pyridine derivatives are thepyridylethyl ethers disclosed in US. 2,667,491; the2-amino-6-thiohydrocarbonpyridines disclosed in U.S. 3,247,214; thepoly-substituted pyridines disclosed in US. 3,252,858; the pyridylthiolcarbonates disclosed in US. 3,284,459; the pyridylthiocarbamatesdisclosed in US 3.284,460; the pyridyl-phosphorodithioic acid estersdisclosed in US. 3,304,226; the esters of pyridine di-carboxylic acidsdisclosed in US. 2,757,120; etc., however, none of the above knownpyridine derivatives is suggestive of the pyridine compounds of thisinvention.

In accordance with one broad aspect of the present invention, there areprovided novel monoand poly-substituted amine derivatives of pyridine.Such pyridine derivates are, in general, characterized by the followinggeneral formulae:

where n can be an integer of from 1 to 4, and X and (A--DZ) can occupyany position of from 2 to 6. When n is 1, X can be any of the followingrepresentative groups:

hydrogen sulfonamido carboxyl benzyloxy imido phosphoramido dialkylaminoalkylsulfoxide keto chlorine alkylthio fluorine cycloalkyl amidocarbamyl alkylamino haloalkyl nitroso iodine mercapto hydroxyl alkylnitro ureido aldehydo trihalomethyl arylthio alkylsulfone When n isgreater than 1, X can be the same or a combination of any of the abovesubstituents, particularly a combination of any of such substituentswith an amino, alkoxy, bromine, chlorine or phenoxy group.

D can be (1) (CH where n is 1-6; (2) (CH G(CH where n is 1-6 and G isNR, 0, )o 2 2)n( )n( z)n, where n is 1 or 2; (4) (CH (C=- =C) (CH wheren is 1 or 2; or (5) an alkyl linkage having from 1-6 carbon atoms and asubstituent (R) located at the terminal or any adjacent carbon atom.

3 e; Z can be NR NR SR, OR. However, when X is ca amino, chloro, oralkoxy and n is 1, Z can be NHR, NR SR, or OR (with A and D being asaforedescribed).

Alternatively, when X is amino, chloro, bromo, alkoxy ea or nitro and nis 1 and A is NH, Z can be NHR, NR SR, or OR (with D being asaforedescribed).

Moreover, when X is phenoxy and n is 1 and A is CH Z can be NHR, NR SR,or OR (with D being as aforedescribed).

Furthermore, when X is hydrogen and n is 4 and A is S, Z can be NR SR,or OR.

The moiety R wherever it appears above is meant to include any of thefollowing: (1) hydrogen; (2) alkyl, comprising aliphatic compoundshaving from 1 to 20 carbon atoms; (3) cycloalkyl, comprising hydrocarboncompounds having from 1 to 20 carbon atoms, includ ing polycyclicsystems, such as, for example, Decalines; 0 (4) aralkyl, comprisingcompounds of the formula: -'(CH (C H )-(X wherein X is as previouslydescribed; (5) aryl, comprising compounds of the formula: (C H )(X,,)wherein X is as previously described; (6) alkenyl, comprising straightorbranched-compounds having from 2 to carbon atoms and from 1 to 4 sitesof unsaturation, at least one of those sites consisting of C Cunsaturation; (7) alkynyl, comprising straightor branched-compoundshaving from 2 to 20 carbon atoms and from 1 to 4 sites of unsaturation,at least one of those sites consisting of CEO unsaturation; and (8)substituted alkyl, comprising alkyl groups, as defined in -(1), beingsubstituted by X type compounds previously described in a manner and/ornature well known to those skilled in the art. 3r

Compounds illustrative and exemplary of the abovedefined novel monoandpoly-substituted amine derivatives of pyridine are described andcontained elsewhere herein, particularly in the examples which followand in the tables included therein.

In accordance with another broad aspect of the present invention, thereare provided novel monoand polysubstituted amide derivatives, includingbenzyloxy amide derivatives, of pyridine. Such pyridine derivatives are,in general, characterized by the following general formulae:

where n can be an integer of from 1 to 4, and X and (ADZ) can occupy anyposition of from 2 to 6. When n is 1, X can be any of the followingrepresentative groups:

When n is greater than 1, X can be the same or a combination of any ofthe above substituents.

A can be 0, NR, S(O) CR O-, CR

D can be (1) (CH Where n is 1-6; (2)

where n is 1-6, and G is NR, 0, S, SO, S0 P=O; (3) (CH ),,(CH=CH),,(CHwhere n is 1 or 2; (4) (CH ),,(CEC),,(CH Where n is 1 or 2; or (5) analkyl linkage having from 1-6 carbon atoms and a substituent (R) locatedat the terminal or any adjacent carbon atom.

Z can be (1) a substituted amino group of the formula where L is wherethe Us can be the same or different and L is -CR ll M and where, in thecase of both and N M is NR, S, or O and R' =NR OR, SR, haloalkyl; L canalso be SOR, or R; (2) OL (L being as just defined in (1)) except that Acannot be oxygen; (3) S--L (L being as just defined in (1)); and (4)Z=phenyl, substituted phenyl, alkenyl, alkynyl, haloalkyl.

The moiety R wherever it appears above is meant to include any of thefollowing: (1) hydrogen; (2) alkyl, comprising aliphatic compoundshaving from 1 to 20 carbon atoms; (3) cycloalkyl, comprising hydrocarboncompounds having from 1 to 20 carbon atoms, including polycyclicsystems, such as, for example, decalins; (4) aralkyl, comprisingcompounds of the formula:

wherein X is as previously described; (5) aryl, comprising compounds ofthe formula: (C H )(X wherein X is as previously described; (6) alkenyl,comprising straightor branched-compounds having from 2 to 20 carbonatoms and from 1 to 4 sites of unsaturation, at least one of those sitesconsisting of C=C unsaturation; (7) alkynyl, comprising straightorbranched-compounds having from 2 to 20 carbon atoms and from 1 to 4sites of unsaturation, at least one of those sites consisting of CECunsaturation; and (8) substituted alkyl, comprising alkyl groups, asdefined in (1), being substituted by X type compounds previouslydescribed in a manner and/ or nature well known to those skilled in theart.

Compounds illustrative and exemplary of the abovedefined novel monoandpoly-substituted amide derivatives of pyridine are described andcontained elsewhere herein, particularly in the examples which followand in the tables included therein.

In accordance with a specific embodiment of the present invention, thereare provided novel monoand poly-substituted pyridine derivatives whichcan be generally classified as (I) aminoalkoxy, aminoalkenoxy, oraminoalkynoxy pyridines and (II) amidoalkoxy, amidoalkenoxy, oramidoalkynoxy pyridines. Such pyridine derivatives can be characterizedby the following general formulae:

where X and D are as previously defined and Z is NH NR or N+R with Rbeing as previously defined.

Xn ODZ" where X and D are as previously defined and Z is a substitutedamino group of the formula where L is ,(I?RI M and R is NR and M is NRor O, with R as previously defined.

In accordance with another specific embodiment of the present invention,there are provided novel monoand poly-substituted pyridine derivativesof the following general formula:

where X,,, D and Z are as previously defined except that X may occupyonly the positions 2, 3, 4, and/or 5 and ODZ may only occupy the6-position. I

In accordance with another specific embodiment of the present invention,there are provided novel di-substituted pyridine derivatives of thefollowing general formula:

xgonz where X and D and Z are as previously defined.

In accordance with another specific embodiment of the present invention,there are provided novel di-substituted pyridine derivatives of thefollowing general formula:

ringed) z where X and D and Z are as previously defined.

In accordance with another specific embodiment of the present invention,there are provided novel 2,6-di-substituted pyridine derivatives of thefollowing general formula:

xflonz where X and D and Z are as previously defined.

In accordance with still another specific embodiment of the presentinvention, there are provided novel 2,6-di-substituted pyridinederivatives of the following general formula:

XOODNBA where X, D, and R are as previously defined.

In accordance with yet another specific embodiment of the presentinvention, there are provided novel 2,6-disubstituted pyridinederivatives of the following general formula:

halogen (O) Xnm S DZ N i i Method B (utilizing a 2-, 4-, and/orfi-halopyridine reactant):

+ M halide I NDZ A, solvent Method C (utilizing a 3-, and/orS-substituted pyridine reactant):

AH Xu I +CZ) Xn Method D:

Xn AD-NRe R Anion AND Ra Anion By means of the following five methods ofsynthesis, moreover, the aforementioned amide derivatives of thisinvention may be prepared.

Method B:

triethylamine 0 (0 L; Xu ADNHR R halogen Method F:

O ADNHR (11%)20 Xn 7 Method G:

X ADNHR RN=C=S l (0) A ISI (0) N N ADNCNR H R O EIJNHR) Method H:

0(5) l Xu ADNH halogen P (OR)2 triethylamine R 0 S ll X ADIIIP (OR)2 Hhalogen Method 1:

triethylamine X ADIIIH halogen SOzR X" ADNSOzR 11 halide In addition tothe foregoing preparative methods set forth hereinabove, an additionalmethod for preparing the N-oxide form of the final product shown abovecan be set forth, for example, as follows:

X ADZ oxidant Xn ADZ In general, the preparative methods for producingthe pyridine derivatives of this invention involve nucleophilicdisplacement of an appropriate displaceable group .from a suitablesubstituted pyridine. The general reaction conditions for these methodsof preparation of the various substituted pyridine derivatives of thisinvention comprise temperatures ranging from about 0 C. to about 200 C.,preferably from about 80 C. to about 130 C. The reaction time may varyfrom about 1 to about 48 hours, depending upon the choice of reactantsand the reaction conditions, but may take as long as about 72 hours.Ordinarily, however, the reaction should take no longer than about 12hours. Various solvents useful in the foregoing methods of preparationinclude such as toluene, benzene, xylene, dimethylformamide,triethylamine, etc.

Exemplary of the foregoing monoand poly-substituted amine and amidepyridine derivatives of this invention are the following compounds,represented by their structural formulae (this list is onlyrepresentative and is not, by any means, intended to be exhaustive):

etc.

As previously noted, the mono-substituted and polysubstituted pyridinederivatives of this invention are use ful as pesticides. One aspect ofsuch pesticidal application is as a herbicide, either pre-emergent orpost-emergent, or as a fungicide. When used as a fungicide or herbicide,the compositions of this invention may be used to control plant growthor fungi thereon by either applying to foliage or plant growth media, agrowthor fungi-controlling dosage of the monoor poly-substitutedpyridine compound or of concentrated compositions prepared by bringingthe aforesaid compound (as an active ingredient) in intimate admixturewith at least one material of the group consisting of finely-dividedinert solids, granular solids, surface active dispersing agents,poly-glycols beeswax, parafiin waxes, water, organic solvents, nitrogenfertilizers, potassium fertilizers, urea, metaphosphates, etc.Particularly contemplated as desirable concentrate compositions arethose which comprise the aforesaid monoor poly-substituted pyridinecompounds as active ingredient in intimate admixture with at least onematerial of the group consisting of finely-divided inert solids, inertgranular solids, and surface active dispersing agents. Another type ofuseful concentrate composition contemplated according to this inventionis the aqueous concentrate composition comprising an aforesaid pyridinederivative as an amine salt.

The expression surface active dispersing agent as herein employed isintended to include all agents which are capable of acting at theinterfacial surface between the aforesaid pyridine derivative orcomposition and water or organic solvents as the dispersion medium,facilitating thereby the dispersion of the toxicant in water or organicsolvents to form aqueous and emulsifiable concentrate. The term isinclusive of solid emulsifying agents such as finely divided bentonite,pyrophyllite, fullers earth, attapulgite, silica, other clays andmineral carriers, as Well as liquid and solid ionic and non-ionicwetting and dispersing agents, alkaline earth metal caseinates, alkylaryl sulfonates, sulfonated oils, complex organic ester derivatives,complex ether alcohols, condensation products of alkylene oxides withphenols and organic acids, poly-oxy ethylene derivatives of Sorbitanesters, mahogany soaps, etc.

Other suitable surface active dispersing agents may be found inDetergents and Emulsifiers, Up to Date, written and published by John W.McCutcheon, Inc., New York, 1962,

The term 'finely divided inert solids as herein employed refers tomaterial whose primary function is not as dispersant of the presentpyridine derivatives in water or organic solvents but as carrier fordust compositions. Illustrative of such carriers are materials such aschalk, talc, gypsum, etc.

The term inert granular solids refers to mineral or other inert carrierswhich are suitable for dry application and which include corn cobs,sand, and other materials which differ primarily in particle size fromthe finely divided inert solids.

According to the present invention, any of the appropriate monoorpoly-substituted pyridine derivatives disclosed herein may be compoundedwith any of the finely divided solids to form dust compositions bygrinding, mixing or wetting the finely divided carrier with a solutionof the toxicant in a volatile organic solvent. Similarly, dustcompositions containing the aforesaid pyridine deri- 'vatives may becompounded from any one or more of the solid surface active dispersingagents previously mentioned, such as bentonite, fullers earth,attapulgite and other clays. Depending upon the proportions ofingredients, these dust mixtures may be employed either as treatingcompositions or as concentrates to be subsequently diluted withadditional solid surface active dispersing agent or with talc, chalk,gypsum, etc., to obtain the desired amount of toxicant in a compositionadapted to be applied to plants, plant growth media or fungi thereon,for the suppression of plant growth or said fungi. Also, suchconcentrate dust compositions may be dispersed in water or organicsolvent with or without the aid of additional dispersing or emulsifyingagents to form spray mixtures.

Dust concentrates, such as above-described, or alternatively appropriatemonoor poly-substituted pyridine compounds may be intimately mixed withliquid or solid ionic or non-ionic dispersing agents to form sprayconcentrates. Such concentrates are readily dispersible in liquidcarriers to form sprays containing the monoor poly-substituted pyridinederivatives in any desired amount.

Any of the monoor poly-substituted pyridine compounds of this inventionmay also be compounded with suitable Water-miscible or water-immiscibleorganic liquid and surface active dispersing agents to produce liquidconcentrates which may be further formulated with water and/or oil toprepare spray mixtures in the form of aqueous dispersions oroil-in-water emulsion compositions. The exact step to be employed inpreparing such compositions is Within the knowledge of those skilled inthe art. Preferred water-immiscible organic liquids include petroleumoil and distillates, toluene, xylene, cumene and other aromatichydrocarbon sol'vents, chlorinated aliphatic hydrocarbons, isoparaflinoil and other aliphatic hydrocarbon solvents. Water-miscible organicsolvents include acetone, methylethyl ketone, cyclohexanone, alcohols,dimethyl fomamide, ether alcohols of ethylene glycol marketed undertrade names such as Dowanol and Cellosolve, and esters such as ethylacetate, secondary butyl acetate and isopropyl acetate. When theaforesaid pyridine derivatives of this invention are alkali metal,ammonium or amine salts, aqueous concentrate compositions are readilyprepared. The salts may be first compounded in a Water-miscible organicsolvent and added to a minimal amount of water, or they may be directlycompounded in 'water or in a water-organic solvent mixture. Usually,

the use of a procedure which includes addition of a small amount of awater-miscible organic solvent is preferred. Moreover, in the case ofsalt compositions, the salt need not be performed but may be preparedduring the compounding process. Thus, the desired monoorpoly-substituted pyridine compound and desired amine or inorganic basemay be mixed together in appropriate amounts in an aqueous organicsolvent mixture.

The present compositions may also contain other plant growth modifyingagents either as adjuvants or supplementary materials for bothterrestrial and aquatic applications.

In carrying out the methods of the present invention, as they pertain tothe control of fungi or of plant growth or vegetation, the monoorpoly-substituted pyridine compounds of this invention are administeredto foliage, plant parts or growth media of the plant species whosepesticide control is desired. The exact amount to be administered varieswith the particular type of growth control to be achieved. It furthervaries with method of application i.e., whether the application is to bemade to foliage, food, flower, or particular plant part, or to soil orother growth media, and the overall site of application: a shelteredarea, such as a greenhouse; or an exposed area, such as fields, etc.Thus, as for example, in the treatment of grass and weeds, soilapplication is preferred to foliage application and the amounts aregoverned thereby. Also, weeds present in sheltered areas are moreresponsive to treatment and minimal dosages are usually adequate whereasfield applications often times require higher dosages to counteractadverse weather effects. An additional factor to be considered is theplant species to be treated, as well as the presence or absence ofdesirable plants together with the undesirable species. Thus, selectivegrass control may be achieved by administering suflicient pyridinederivaties of this invention to irradicate grasses Without affectingbroad leaf.

Effective control of terrestrial plants in soil may be readily achievedby the administration of various pyridine derivatives of this invention.

The administration of the present compounds or compositions thereof toplant or plant growth media may be carried out in any manner known tothose skilled in the art and may be carried out by using dustcompositions, sprays or any other modification provided that aneffective dosage is supplied. It is to be understood that the totalvolume or weight of the treating compositions to be employed is notcritical so long as the critical amount of the aforesaid pyridinecompounds is supplied. Frequently, the desirability of a moreconcentrated or dilute composition depends upon the method ofapplication and the area to be covered; hence, the selection of theconcentration and total volume or weight may be made by those ofordinary skill in the art of the foregoing teachmgs.

While the aforementioned discussion has focused upon the use of theaforesaid pyridine compounds of this invention as fungicides orherbicides, they may also be used as nematocides or insecticides byformulating such insecticides or nematocides from said monoorpoly-substituted pyridine compounds of this invention in any suitableform, such as: a solution, dust, emulsion, suspension, aerosol, fog orthe like, or as a pure compound. Solvents or carriers found suitable inthis regard include those which are substantially inert with respect tothe active repellent ingredient. Among these materials, which are usefulfor this purpose, are acetone, kerosene, naphtha, and other liquidhydrocarbons boiling preferably above atmospheric temperature. Solidinert carrier materials are also contemplated and utilized, such as, forexample, talc, kieselguhr, and other inert carriers, when preparingdust. The active insect repellent or nematocide ingredients of thisinvention may be applied in the form of an aqueous emulsion ordispersion preferably when employing a wetting or dispersing agent, as,for example, Triton X-100 (an alkylated aryl polyether alcohol), Tween20 (a sorbitan monolaurate polyoxyethylene derivative), etc. In someinstances, the active ingredient can be as advantageously applied as thepure compound without a carrier of any kind.

The present invention is further illustrated in greater detail by thefollowing examples, but it is to be understood that the presentinvention, in its broadest aspects, is not necessarily limited in termsof the specific temperatures, residence times, separation techniques,and other process conditions by which the compounds and/or compositionsdescribed and claimed are prepared and used.

In the following examples, the compounds prepared in Examples 1-84 areincluded in Tables 1(a) and I(b) and the nomenclature of each of thecompounds included in Examples 1-84 is included in Table I(c). Thecompounds prepared in Examples 85-148 and the nomenclature there of areincluded in Table II(a). The methods of preparation by which each of thecompounds shown in Examples 1-148 is prepared as designatedalphabetically from A-I inclusive. The general experimental proceduresof Methods A-I are included herebelow.

EXPERIMENTAL PROCEDURES Method A The'metal salt of the appropriatealcohol or thioalcohol was combined with a solution of the properlysubstituted 2, 4 or 6 mono-, dior tri-halo pyridine in an appropriatesolvent (toluene, xylene, dimethylformamide) and heated to reflux forfrom 2 to 48 hours, filtered and evaporated to yield a material whichwhenever possible was either distilled or crystallized to yield thedesired product.

Method B The amine compound was combined with a solution of the properlysubstituted 2, 4 or 6 mono-, dior trihalopyridine in an appropriatesolvent (toluene, xylene, dimethylformamide) containing potassiumcarbonate and potassium iodide and heated at reflux for from 2 to 48hours, filtered, evaporated and the resulting material either distilledor crystallized to yield the desired product.

Method C The appropriate 3 or 5 monoor disubstituted pyridine was heatedwith the appropriate cyclic molecule in the proper solvent in thepresence of acid for from 2 to 48 hours. The solution was neutralizedand evaporated to yield a material which whenever possible was distilledor crystallized to yield the desired product.

Method D The appropriate pyridylamine was combined with the properalkylating agent in an inert solvent such as ether, benzene, acetone,etc. The precipitated product was then removed by filtration andwhenever possible crystallized to yield the desired derivative.

Method E The appropriate acyl halide was added as a solution or in itspure state dropwise to a solution containing the pyridylamine or alcoholand triethylamine in the appropriate solvent (ether, benzene, toluene,acetone, etc.) maintained from -40 to 0 C. The reaction was allowed tobe stirred at room temperature or refluxed from 2 to 48 hours, filteredand the resulting solution evaporated and whenever possible the productwas crystallized from an appropriate solvent or distilled to yield thedesired product.

Method F The appropriate pyridyl alcohol or amine, and anhydride werecombined in the proper solvent (ether, benzene, toluene, etc.) andrefluxed from 2 to 48 hours, washed with base and evaporated to yield aproduct which whenever possible was crystallized or distilled to yieldthe desired product.

Method G The appropriate isocyanate or isothiocyanate was added dropwisein solution or in its pure state to a solution of the pyridyl amine oralcohol in the proper solvent (ether, benzene, toluene, etc.) and afterthe exothermic reaction subsided the solution or suspension was refluxedfrom 2 to 48 hours and the solvent removed under vacuum to yield aproduct which whenever possible was crystallized to yield the properderivative.

Method H The appropriate halophosphate or halothiophosphate was addeddropwise in its pure state or as a solution at room temperature to asolution of the pyridyl amine or alcohol and triethylamine in the propersolvent (ether, toluene, Xylene, etc.) and after the usual exothermicreaction brought to reflux from 2 to 48 hours, filtered, evaporated andwhenever possible the product was either distilled or crystallized toyield the desired derivative.

Method I The appropriate sulfonyl halide was added to Method E.

TABLE I a C1 N -0CHzOH2-R B1 OCH2CH2R Phys. Example Method prop., No.Compound R of prep. C.

ll 1 A NHOH E 3, 63-64 I? 2 B NHCH E s, 70-71 I? s A NHCCH F 8, 73-74 u4 B NHCCH3 F s, 73

ll 5 A NHCCH OH; F s, 76-78 6 B NHOCH2CH3 F s, 83

ll 7 A NHCCHQOHzCHQ F 8, 64-46 s B Nliilcmcmcm F s, 73

l 9 A NH- E 3,127-129 i1 10 B NHC- l E 8,130-134 o 11 A NHi'J-CHWHQ: Fs, 97-98 F 12 B NH( JCH(CH,) F s,112-114 TABLE I(a)-Continued Phys.Example Method prop., No. Compound R of prep. C.

[I 13 A NHOG(OH 0 151 E S, 72-76 1? 14 B NHCC(OH )C H E S, 92-94 I 15 ANHKCHghC-Ha E S, 57-59 H 16 B NHC(CH2)sC-H E S, 63-65 0 ll 17 A NH E s,124-126 0 ll 18 B NE E S, 131-133 H 19 A -NHC E s, 102-103 0 3 20 B -NHE S, 124-125 H 21 A NHC 011701 E 3, 73-75 ll 22 B NHC 011101 E S, 78-80H 23 A NHOC C13 E S, 47-50 ll 24 B NBC 0 013 E S,

ll 25 A NHCCH=CH E S, 127-129 H 26 B NHCOH=OH E S, 112-114 0 27 ANHJIlqS E S, 103-104 0 (l 28 B NH 4) E S, 99-101 1 29 A NlEKlO CH(CH3)2E S, 58-62 7 30 B NH!) O CH(OH E S, 54-55 H 31 A NHON(CH3)2 E S, 171-174I! 32 B NHCN(CH3)2 E S, 60-62 1? 33 A NHCNHCHE G S, 138-140 R 34 BNHNHCHa G S, 146-149 ll 35 A N(CH )CNHCH3 G S, 71-73 7 36 B N(OH )CNHCH3G S, -86

H 37 A NHCNH G S, 133 436 TABLE I(b)Continued Example Method Phys. No.Compound of prep. prop, C. 79 CgIIaOQ-OCIEOII) A L, 124-133.

80 01 i NHCHN, A S 59-91.

81 0 1150 N O CH A L, 109.

82 CHzO- A S, 74-75.

qSCHzO 84 01 N -SCHM: A L, 145460.

1 At 1.0 mm. 2 At 0.5 mm. 3 At 0.3 mm. 4 At 0.025 mm. 5 At 0.1-.6 mm.NoTE.S=S0lid; L=Liquid.

TABLE I(c) 2-chloro-6 2-formamidoethoxy pyridine 2-br0m0-6Z-forrnamidoethoxy) pyridine 2-chloro-6 Z-acetarnidoethoxy) pyridine2-bromo-6 2-acetarnidoethoxy pyridine 2-chloro-6 2-propionarnidoethoxy)pyridine 2-bromo-6 2-propionamidoethoxy) pyridine 2-chlor0-6Z-butyramidoethoxy) pyridine Z-bro mo-6 (Z-butyrarnidoethoxy) pyridine2-chloro-6 2-cyclopropylcarboxamidoethoxy) pyridine 2-bron10-62-cyclopropy1carb oxamidoethoxy) pyridine 2-chloro-62-isobutyramidoethoxy) pyridine 2-b rom0-6 (2-isobutyramidoethoxypyridine 2-chloro-6 2-decanarnidoethoxy) pyridine 2-bromo-6Z-decanamidoethoxy) pyridine 2-chloro-6 2-cyclohexylcarboxamidoethoxy)pyridine 2-br0m0-6 2-cyclohexylcarboxamidoethoxy) pyridine 2-ch1or0-6 [2l-methylvalerarnido ethoxy] pyridine 2-br0mo-6 [2 l-methylvaleramidoethoxy] pyridine 2-chloro-6 2-cyclobutylcarboxamidoethoxy pyridine2-brorno-6 2-cyclobutylcarboxarnidoethoxy pyridine 2-ch10r0-6 [2l-chloroacetamido ethoxy] pyridine 2-bromo-6 [2 l-chloroacetarnidoethoxy] pyridine 2-ch1oro-6 [2( 1, 1 l-trichloroacetamido ethoxy]pyridine 2-bromo-6 [2( 1, 1, l-trichloroacetamido) ethoxy] pyridine2-chloro-6 2-cinnamidoethoxy) pyridine 2-bromo-6 (Z-cinnarnidoethoxy)pyridine 2-ch10ro-6 (Z-benzamidoethoxy) pyridine 2-bromo-62-benzamidoethoxy pyridine 2-chloro-6 2-isopropoxycarboxarnidoethoxypyridine 2-br0m0-6 2-isopropoxycarboxamidoethoxy) pyridine 2-chlor0-6Z-dimethylaminocarboxamidoethoxy) pyridine 2-brorno-6Z-dimethylarninocarboxarnidoethoxy pyridine 2-chloro-6(2-methy1aminocarboxamidoethoxy) pyridine 2-brorno-6(Z-methylaminocarboxamidoethoxy pyridine 2-chloro-6 [Z-rnethylamino(N-methyl carboxamidoethoxy] pyridine 2-bromo-6 [Z-methylamino (N-methylcgrbpgrarnidqethoxy] pyridine 2-ch1oro-6 (2-ani1inocarboxamidoethoxy)pyridine 2-bromo-6 Z-anilinocarboxamidoethoxy) pyridine 2-chloro-62-succinamidoethoxy) pyridine 2-br0m0-6 2-succinamidoethoxy) pyridine2-ch10ro-6( 2-propanesulfonamidoethoxy) pyridine 2-brorno-6(2-propanesulfonamidoethoxy pyridine 2-ch1oro-62-benzenesulfonamidoethoxy) pyridine 2-br0mo-6(Z-benzenesulfonamidoethoxy) pyridine 2-chloro-6[2(4-methyl-benzenesulfonamido ethoxy] pyridine 2-bromo-6[2(4-methylbenzenesulfonamido ethoxy] pyridine 2:hloro-6[2-anilino(N-methy1)carboxarnidoethoxy] pyridine 2-bromo-6[Z-anilino (N-methyl) carboxamidoethoxy] pyridine 2-chloro-6(Z-methacrylamidoethoxy pyridine 2-bromo-6 (Z-methacrylarnidoethoxy)pyridine 2-chloro-6 2-diethoxythiophosphoramidoethoxy) pyridine2-bromo-6 (2-diethoxythiophosphorarnidoethoxy) pyridine 2-chloro-6(2-diethoxyphosphoramidoethoxy) pyridine 2-bromo-6Z-diethoxyphosphoramidoethoxy) pyridine 2-chloro-6- [2(Z-butyramidoethoxy) ethoxy] pyridine 2- (Z-butyramidoethoxy)-5-iodopyridine 2- (Z-butyramidoethoxy -3 -nitropyridine 2-(Z-butyramidoethoxy) -5-nitropyridine 2-ethoxy-6 Z-butyramidoethoxy)pyridine 2-chloro-6 (2-butyramido-Z-methylpropoxy pyridine 2-chloro-6(4-butyramidobutoxy pyridine 2-chloro-6( 1-phenyI-Z-butyramidoethoxy)pyridine 2-bromo-6 1 -phenyl-2-butyramidoethoxy pyridine 2-methy1-6(Z-butyramidoethoxy) pyridine 2-bromo-6 (2-butyramid0-2-methylpropoxy)pyridine 2- (Z-butyramidoethoxy) -5-chloropyridine 2-(2-butyramidoethoxy) -5-brornopyridine 2- (Z-butyramidoethoxy-3-ch1oropyridine 2-ch10r0-6 (Z-butyramidoisopropoxy) pyridine 2-brom0-62-butyramidoisopropoxy) pyridine TABLE II(a)-Cntinued Example S=Solid,L=Liquid No. Compou pd formula Name Phys. Prop., 0. Method 1092-(2-methylaminoethoxy)pyridine L, 69-70 at 0.1 mm A \N O CH2CH2NHCHg0112011 0111 110 -0-OH-CHz-N 2-(1-N-aziridy1-2-butoxy)pyridine L, -91 at0.1 mm A CH] 111 O OHgCH2N\ l 4-(2-N-aziridy1ethoxy) pyridine L, -115 at0.02 mm A 112 N O OH2CH2NH2 2-(2-aminoethoxy)pyridiue L, 63455 at 0.05mm A /CH 113 OCH2CH3CH2N 2-(3dimethylamino-n-propyloxy)pyridine L, 80-83at 0.1 mm A /C H 114 -O CHQCHQN Z-Z-dimethylaminoethoxy)pyridine L,50-51 at .01 mm A 1 115 Q-O-O Or-C-OHr-N2-1-phenoxy-3-(2,2-dimethy1-N-aziridy1)2- L, undistilled A lpropyloxflpyridine. O\ (3-0 H;

116 2-(3-methoxypropy1amino)pyridine L, 77-79 at 0.05 mm B N NH(CH2)3OCH3 117 H 2-(2-methoxyethy1amino)pyridine L, 76-86 at 0.1 mm B NN(CH,):O C 3 118 H 2-(2-ethoxyethyI-amino)pyridine S, 36-37 B 119 NHn2-(2-aminoeth0xy)-3-aminopyridine L, 126-135 at 0.03 mm A.

N --O(CH2)2NH 120 /CH1 2-(2-N -aziridyletl1oxymethyl) pyridine L, 85-90at 0.02 m.m A

\N/ CH;O OH CHgN CH: /OH 0 H2O CHzCHzN CH3 1214-picolyl-Himethylammoethylether L, 85-90 at 0.01 mm A TABLEII(a.)-Continued Example S Solid, L Liquid 0. Compound formula NamePhys. Prop., 0. Method 135 2-bromo-6(l-phenyl-2-aminoetl1oxy)pyridine doA BI-\N O CH CH2HN2 136 2-methyl-6(2-aminoethoxy)pyridine L, 53-60 at0.05 mm A OH N O CHzCHzNHz 137 2-bromo-6(2-aminoethoxy)pyridine L, 96 at0.1 mm A Br- N l O CHaCHzNHz 138 2-chloro-6(3-amino propoxy pyridine L,110-114 at .05.1 mm. A

139 Y 2-bromo-6(3-amino propoxy) pyridine L, 105-115 at .01-.1 mm- A B1\N 0 (CH2) gNHz Cl 140 2(Z-aminoethoxy)-3-chloropyrirline R A *0 0 H2CHgNHg 141 I 2-ch1oro-6(2-aminoisopropoxy)pyridine L, 80-86 31170.6 mm AO OH(OH CH NH 142 I 2-chloro-6(2-ami.noethoxy)ethoxypyridine L, 104-114at .05-.07 mm... A

0 (013:)20 (OHzhNH 143 l 2-0h1oro-6(2-methylaminoethoxy)pyridine L,75-85 at .2-.3 mm..- A

01 N O(CH2)2NHCH l 144 EtO- O (CHz)zN (CH3)a2-eth0xy-6(Z-trimethylaminoethoxy)pyridine-.... S, 258-260 D 145 012(Z-aminoethoxy)-5-ohloropyridine S, 57-59 A N O OHzCHzNHz 146 OH2Ol-OCHzOHzNHa 2-benzyloxy-S-(2-aminoethoxy)pyridine S, 114 A 147 Br2(2-aminoethoxy)-&bromopyridine S, 97-101 A N OCH2CH2NH2 1480(CH2)2N(UHa)3 'I 2-ohoo-6(2-trimethylaminoethoxy)pyridine S, 197-200 DEXAMPLE 149 In this example, 2-chloro-6-benzylthio-pyridine was preparedby the following experimental procedure.

To a solution of sodium ethoxide (271 g.; .35 mole) in 250 ml. ofethanol was added dropwise benzyl mer- 70 stir overnight and the ethanolwas distilled 01f at atmospheric pressure. To the resulting paste wasadded 200 ml. of toluene and the mixture brought to reflux. A solutionof 2,6-dichloropyridine (44.3 g.; 0.3 mole) in 60 ml. to toluene wasadded rapidly to the refluxing mixture captan (37.0 g.; 0.30 mole). Themixture was allowed to 75 and allowed to reflux overnight. The cooledmixture was partitioned between chloroform and water and the organiclayer dried with magnesium sulfate, filtered, and evaporated in vacuo toyield a thick oil which was vacuum distilled to yield2-chloro-6-benzylthiopyridine B.P. 145150.

AnaIysI' .Calcd. for C H ClNS (percent): C], 15.1; S, 13.6. Found(percent): Cl, 14.69; S, 13.8.

EXAMPLE 1 0 In this example, several compounds exemplified in Table Iwere tested as soil fungicide in accordance with the following testprocedure. The results of this test are shown in Table III.

The test Organisms, which were Rhizoctonia, Pythium, Fusarium andSclerotium, were raised in sterile soil cultures to which corn meal wasadded. The soil used for dilution purposes was separately sterilizedwith methyl bromide. The soil used for test purposes was prepared bymixing 10% by weight of infested soil with 90% by weight of thesterilized soil. The test soil was then apportioned in 50 gramquantities to four paper cups for each organism. The soil was treatedwith a candidate chemical by drenching each cup separately with 10 ml.of a candidate material prepared 32 following test procedures. Theresults of this test are shown in Tables IV and V.

Test procedure for measuring pre-emergent herbicidal activity Flats wereplanted to the desired crops to a depth of approximately /2 inch. Thecrops employed were pigweed, crabgrass, foxtail, mustard, Johnson grass,cotton, soybean, oats, corn, tomato, morning glory, and lambsquarter.The chemicals were initially screened at a dosage of 10 lbs. of activeingredient per acre. Candidate materials as wettable powders wereextended in water and 250 ml. of such a suspension uniformly distributedover each fiat. The flats were immediately transferred to the greenhouseand covered for a period of three days so that additional watering wasnot required until some of the plants began to make their appearanceabove the ground. The flats were then held for 21 days before recordingemergence and final phytotoxicity effects was affected. Phytotoxicitydata were recorded on a scale of 0 to 10 in which 0 indicated no injuryand 10 indicated the plant was killed. Karmex is used as a standard inthis test.

TABLE IV Lbs. Soy- Pig- Moring Lamb's J ohnson Cmpd acre Cotton beanTomato Corn Oats weed Mustard Glory quarter grass 36 10 0 3 7 2 5 9 10 810 0 8 10 8 8 9 5 5 8 10 10 10 10 7 l0 7 J 10 7 6 10 10 10 10 J 10 9 S)10 7 7 10 10 10 l0 10 Karmox 2 2 6 10 4 4 10 10 1O 10 7 1 Karmcx is(also known as Diuron) 3-(3A-dichlorophenyi)-1,1-dimethylurea.

as a 50% wettable powder. The chemical concentration was adjusted togive a dosage of 100 p.p.m. based on weight of the soil. The cups ontrays were then held in the constant temperature-humidity chamber forthe duration of the test. In the absence of control, masses of whitemycelia developed on the surface of the test vessel and control wasreadily evident by the absence of such growth. A rating scale of 0 to 10was used, in which 0 was indicative of no control of the growth orcomplete coverage of the soil surface and 10 was indicative of completecontrol or no mycelial growth.

TABLE III Test procedure for measuring post-emergent herbicidal activityThe crops employed in this post-emergence herbicidal evaluation werepigweed, crabgrass, foxtail, mustard, Johnson grass, cotton, soybean,oats, corn, tomato, morning glory and red kidney beans. Cotton wasnormally in the 46 week stage at the time of spray application. Thekidney beans had well expanded sets of first true leaves. Tomatoes werenormally two weeks of age. Johnson grass was approximately 2 inches inheight. Chemicals were Cmpd formulated as 50% wettable powders andextended in 1 9 36 C t H water to the desired concentration. Candidatematerials 2 on m were screened at 5 lbs./ acre active ingredientcalculated on Dose (ana broadcast basis. The plants were normally scoredfor 100 10g 100 100 phytotoxicity 10-12 days after spray application.Phyto- 0 6 m toxicity ratings were based on a scale of 0-10, in which 08 4 0 8 indicated no injury and 10 indicated that the plants wereSclerotium 0 s 6 8 killed. Diuron is used as a standard in this test.Fusarium 8 4 0 8 l Lanstan is 1-Cl1l0r0-2-11itl0p10pa110.

TABLE V L Soy Pig- Morning Red kid- Crab- Fox- Johnson Cmpd acre Cottonbean Tomato Corn Oats weed Mustard glory ney bean grass tall grass 5 2 410 0 0 2 10 10 8 0 0 0 5 2 5 10 0 2 4 9 s 4 8 s 7 7 5 4 4 10 2 4 4 8 s 75 2 6 21. 5 3 s 10 2 2 6 9 6 7 9 9 s 5-. 5 6 10 10 10 1 8 9 s 10 5 9 5Karmex 2 6 8 10 9 4 10 10 10 10 9 10 8 EXAMPLE 15 1 In this example, 8difierent compounds selected from Tables I and II were tested forherbicidal activity, both EXAMPLE 152 In this example, several compoundsexemplified in Table II were tested as insecticides by exposure ofpre-emergent and post-emergent, in accordance with the Drosophilamelanogaster and Tribolium confusum to a 33 film of each of thecompounds designated on the walls of 200 ml. test tubes.

Drosophila cultures were carried in a routine manner under controlledtemperature and humidity conditions. Their breeding and rearing cyclewas handled in a manner to assure testing of adults of uniform age. Thetest materials were deposited within the test tubes (25 mm. x 200 mm.)in a volatile solvent, such as acetone, and immediately mechanicallyrotated to obtain a thin film of the toXicant on the walls of the testvessels. Ten flies were released into each tube and then stoppered withan absorbent cotton plug holding a protruding tip (dental gum)impregnated with sutficient liquid food to carry them for three days.The dose was 1000 p.p.m.

The test specimens were observed continuously for the first few minutesto determine whether the candidate material possessed knockdownproperties. Routine counts were then made at 24 and 48 hour intervalsand reported as percent mortality.

It is to be noted that the above test can also very readily be modifiedin procedure to evaluate the residual activity of a material as a thindeposited film; in this event, the film would merely be aged for therequired period of time before releasing the flies into the test vessel.

The general test procedure of evaluating the designated chemical forinsecticidal activity against Tribolium confusum was as follows: First,the chemical to be used was prepared in the form of a 0.1% acetonesolution if the materials were acetone soluble. 2 ml. of the chemical tobe tested was then deposited uniformly over the floor of a 4 oz. glassjar and the acetone was permitted to evaporate off, leaving a thin filmof chemical. Adult confused flour beetles, priorly starved fortwenty-four hours, were then placed, ten per jar, on duplicate testvessels. Unless otherwise indicated, the jars were closed during theduration of observation. The dosage was equivalent to 46 mgms. persquare foot.

The insects were then examined frequently over the first few hours toobserve the efiYect of the chemicals on their behavior so far asknockdown and rapidity of action was concerned. Notes were made on anyunusual reactions, such as agitation, paralysis and the approximate timefor such effects to occur. Mortality counts were made over a period of 1and 2 days, respectively.

The results of these tests are shown in Table VI.

TABLE VLPERCENT MORTALITY Confused flour Drosophila beetle Dose, Cmpd.p.p.m. 24 hrs. 48 hrs. 24 hrs. 48 hrs.

108 1,000 100 100 100 100 101 1, 000 0 95 100 Kelthane 1 1, 000 100 100100 100 1 Kelthane is 1,1-bis (p-chlorophenyl)-2,2,2-trichloroethanol.

EXAMPLE 1 5 3 In this example, the nematocidal activity of thecompounds, tested was determined against a species of Panagrellus, anactive saprozoic nematode, in accordance with the following testprocedure. The results of this test are shown in Table VII.

TABLE VII Percent kill Dose, Ompd p.p.m. 24 hr. 72 hr. 120 hr.

500 100 100 100 500 100 100 100 N emagon 1 500 100 100 100 1 Nemagon is1,Z-dibromo-3-ehloropropane.

34 duplicate and the check or blank contained nema in tap water. To benoted is the fact that the nematodes, when properly handled, can surviveat least seven days in the blanks without the addition of food. Dosagelevels were 500, 50 and 5 p.p.m.

Microscopic observations on the behavior of the nema were made dailyover a period of five to seven days to establish the rapidity of actionof the chemical and the final end point of kill. The constant and activemovement of this species, however, permitted easy identification of liveand dead individuals.,The rapid and short cycle of reproduction byparthenogensis permitted observation of the effect of the chemicals onreproductive behavior and also on individuals of different ages.

It is thus seen that the compounds of this invention are useful asherbicides, fungicides, insecticides and nematocides. The methods ofapplication in which the monoor poly-substituted compounds of thisinvention are employed as herbicide, fungicide, insecticide ornematocide, have been discussed previously in the description of thisinvention.

While the invention has been described with a certain degree ofparticularity, various modifications can be made therein withoutdeparting from the scope of this invention as defined by the followingclaims.

What is claimed is:

1. A compound having the following structure X is selected from thegroup consisting of hydrogen,

halogen and lower alkoxy; A is selected from the group consisting of-NHR O and OR wherein R is lower alkylene wherein R is lower alkyl, halis a halide anion;

y is the integer 1 or 2 with a proviso that when (ADZ) represents theradical, X is other than halogen.

2. The compound according to claim 1 wherein the specific compound is2-chloro-6(2 methoxy propylamino) pyridine.

3. The compound according to claim 1 wherein the specific compound is2-chloro-6(2 hydroxyethylamino) pyridine. Y

4. The compound according to claim 1 wherein th specific compound is2-ethoxy-6(Z-trimethylaminoethoxy) pyridine iodide.

5. The compound according to claim 1 wherein the specific compound is2-methoxy-6(2-methylaminoethoxy) pyridine.

6. The compound according to claim 1 wherein the specific compound is2-chloro-6(2-aminoethoxy)pyridine.

7. The compound according to claim 1 wherein the specific compound is2-ethoxy-6-(2-aminoethoxy)pyridine.

8. The compound according to claim 1 wherein the specific compound is2-bromo-6-(3-methoxypropylamino) pyridine.

9. The compound according to claim 1 wherein the specific compound is2,6-di(Z-trimethylaminoethoxy) pyridine diiodide.

10. The compound according to claim 1 wherein the specific compound is2-bromo-6-(Z-ethoxyethylamino) pyridine.

11. The compound according to claim 1 wherein the specific compound is2-bromo-6-(Z-methylaminoethoxy) pyridine.

12. The compound according to claim 1 wherein the specific compound is2-bromo-6-(3-methoxypropylamino) pyridine.

13. The compound according to claim 1 wherein the specific compound is2,6-di(Z-dimethylaminoethoxy) pyridine.

14. The compound according to claim 1 wherein the specific compound is2,6-di(3-dimethylaminopropyloxy) pyridine.

15. The compound according to claim 1 wherein the specific compound is2,6-di(Z-methylaminoethoxy)pyridine.

16. The compound according to claim 1 wherein the specific compound is2,6-di(2-aminoethoxy) pyridine.

17. The compound according to claim 1 wherein the specific compound is2-ethoxy-6-(Z-methylaminoethoxy) pyridine.

18. The compound according to claim 1 wherein the specific compound is4-(2-dimethylaminoethoxy)pyridine.

19. The compound according to claim 1 wherein the specific compound is2-(2-methyl aminoethoxy)pyridine.

20. The compound according to claim 1 wherein the specific compound is2-(2-aminoethoxy)pyridine.

21. The compound according to claim 1 wherein the specific compound is2-(3-dimethylamino-n-propyloxy) pyridine.

22. The compound according to claim 1 wherein the specific compound is2-(Z-dimethylaminoethoxy)pyridine.

23. The compound according to claim 1 wherein the specific compound is2-(3-methoxypropylamino) pyridine.

24. The compound according to claim 1 wherein the specific compound is2-(2-methoxyethylamino)pyridine.

25. The compound according to claim 1 wherein the specific compound is2-(2-ethoxyethylamino)pyridine.

26. The compound according to claim 1 wherein the specific compound is2-(Z-aminoethoxy)-3-aminopyridine.

27. The compound according to claim 1 wherein the specific compound is2-(2-N-aziridylethoxymethyl)pyr- 36 specific compound is2-(Z-trimethylaminoethoxy) pyridine iodide.

34. The compound according to claim 1 wherein the specific compound is2,6-di(3-trimethylaminopropoxy) pyridine diiodide.

35. The compound according to claim 1 wherein the specific compound is2-chloro-6-(2-methyl-2-aminopropyloxy)pyridine.

36. The compound according to claim 1 wherein the specific compound is2-bromo-6-(2-methyl-2-aminopropyloxy)pyridine.

37. The compound according to claim 1 wherein the specific compound is2-chloro-6-(4-aminobutoxy)pyridine.

38. The compound according to claim 1 wherein the specific compound is2-chloro-6-(1-phenyl-2-aminoethoxy)pyridine.

39. The compound according to claim 1 wherein the specific compound is2-bromo-6-(1-phenyl-2-aminoethoxy)pyridine.

40. The compound according to claim 1 wherein the specific compound is2-methyl-6-(2-aminoethoxy)pyridine.

41. The compound according to claim 1 wherein the specific compound is2-bromo-6-(2-aminoethoxy)pyridine.

42. The compound according to claim 1 wherein the specific compound is2-chloro-6-(3-aminopropoxy) pyridine.

43. The compound according to claim 1 wherein the specific compound is2-bromo-6-(3-aminopropoxy)pyridine.

44. The compound according to claim 1 wherein the specific compound is2-(2-aminoethoxy)-3-chloropyridine.

45. The compound according to claim 1 wherein the specific compound is2-chloro-6-(2-aminoisopropoxy) pyridine.

46. The compound according to claim 1 wherein the specific compound is2-chloro-6-(Z-aminoethoxy)ethoxypyridine.

47. The compound according to claim 1 wherein the specific compound is2-chloro-6-(2-methylaminoethoxy) pyridine.

48. The compound according to claim 1 wherein the specific compound is2-ethoxy-6-(Z-trimethylaminoethoxy pyridine.

49. The compound according to claim 1 wherein the specific compound is2-(Z-aminoethoxy)-5-chloropyridine.

50. The compound according to claim 1 wherein the specific compound is2-benzyloxy-6-(Z-aminoethoxy) pyridine.

51. The compound according to claim 1 wherein the specific compound is2-(Z-aminoethoxy)-5-bromopyridine.

Schuler et al.: Chem. Abstracts, vol. 60, par. 14, 515, 1960.

ALAN L. ROTMAN, Primary Examiner US. Cl. X.R. 7194; 260294.8 295;424263, 2 66

6. WHEN N IS 1, X CAN BE HYDROGEN, CARBOXYL, IMIDO DIALKYLAMINO, KETO,ALKYLTHIO, CYLOALKYL, PHOSPHORAMIDO, UREIDO, HALOALKYL SUCH AS ASTRIHALOMETHYL, HALOGEN SUCH AS CHLORINE, FLUORINE, OR IODINE, HYDROXYL,AMINO, NITRO, ALDEHYDO, ARYLTHIO, ALKOXYL, PHENOXYL, CARBAMYL,ALKYLSULFOXIDE, NITRILE, AMIDO, ALKYLAMINO, NITROSO, MERCAPTO, ALKYL,SULFONAMIDO, BENZYLOXY, ALKYLSULFONE, ETC. WHEN N IS GREATER THAN 1, XCAN BE THE SAME OR A COMBINATION OF ANY OF THE ABOVE SUBSTITUENTS.RELATIVE TO THE A-D-Z SUBSTITUENT, (I) A CAN BE O, NH, NR, NR2, S(O)0-2,CR2O-, CR2, ETC., (II) D CAN BE ANY OF THE FOLLOWING: (A) (CH2)1-6, (B)(CH2)NG(CH2)N WHERE N IS 1-6 AND G IS NR, O, S, SO, SO2, AND P=O, (C)